The addition of a small excess of triethyl orthoformate to an alcoholic mixture of NiCl[subscript 2]·6H[subscript 2]O and triphenylphosphine (PPh[subscript 3]) results in an increase in the typical isolated yield of [NiCl[subscript 2](PPh[subscript 3])[subscript 2]] from below 50% to over 85%. The impact of water when present in the reaction medium in this system is discussed, and results from the application of the same synthetic approach to the syntheses of [NiBr[subscript 2](PPh[subscript 3])[subscript 2]], [NiCl[subscript 2](dppe)], and [NiBr[subscript 2](dppe)] are presented. A simple synthesis of NiCl[subscript 2]·2H[subscript 2]O by the dehydration of NiCl[subscript 2]·6H[subscript 2]O at 80°C can be performed as an optional step to decrease the quantity of triethyl orthoformate required for the preparation of [NiCl[subscript 2](PPh[subscript 3])[subscript 2]] and/or [NiCl[subscript 2](dppe)]. The experiments are flexible and accommodate a variety of laboratory schedules and student skill levels. Each synthesis can be readily completed within a 3 h laboratory period.